JPH0343309B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD This invention relates to single-component products that exhibit improved stability during storage in the absence of moisture and that crosslink in the presence of moisture at ambient temperatures (i.e., generally 5-35°C). The present invention relates to an organopolysiloxane composition and a method for producing the same. Compositions of this type are referred to below as CVE compositions (cold vulcanizable elastomeric compositions). These compositions are primarily made by mixing hydroxylated diorganopolysiloxane polymers, fillers, certain polyalkoxylated silanes, organic or organosilicon amino compounds, and metal or organometallic carboxylates or chelates. . [Prior Art] Compositions prepared by mixing components similar to those described above are known. Some of these compositions are unstable on storage. Therefore,
These are due to the fact that they need to be packaged as two different packages, for example hydroxylated diorganopolysiloxane polymers, fillers and polyalkoxylated silanes on the one hand and amino compounds and metal salts on the other. , two-configuration type (2
packaging system) composition. This dual packaging condition requires careful mixing of the contents of one package with the contents of the other package only at the time of use, and the resulting entire composition must be used immediately. In this respect, it is less practical, especially in architectural applications, which are most often carried out in open air. Compositions of this type are particularly described in Belgian patent no. 774830
No. 2,152,908 and French Patent No. 2,228,814. Belgian Patent No. 774830 describes hydroxylated or alkoxylated diorganopolysiloxanes,
an alkoxylated silane (or polysiloxane) containing at least one aminoalkyl group and at least one
A composition prepared by mixing a linear aminoalkylpolysiloxane containing alkoxy groups and a curing catalyst is described. French Patent No. 2152908 discloses that a hydroxylated diorganopolysiloxane, an alkoxylated silane (or polysiloxane), a filler, an aminoorganosilane containing hydrolysable groups and a curing catalyst are prepared by mixing. A composition is described. French Patent No. 2228814 describes the mixing of a hydroxylated diorganopolysiloxane, a methylpolysiloxane resin, a filler, an alkoxylated aminoorganosilane (or aminoorganopolysiloxane) and optionally an alkyl silicate or an alkyl polysilicate. Compositions made by the method are described. Some other compositions are stable on storage.
These are known as monolithic compositions,
Packaged in a single package. Compositions of this type are described, for example, in US Pat. No. 3,161,614
No. 3170894, No. 3686357, and JP-A-53
-Described in No. 102956. U.S. Patent Nos. 3,161,614 and 3,170,894 include
Compositions are described that are prepared by mixing a diorganopolysiloxane blocked at each end of the chain with polyalkoxysiloxy units and a curing catalyst such as an organic or organosilicon amine. However, these compositions primarily use diorganopolysiloxanes that are difficult to obtain and are obtained by reacting hydroxylated diorganopolysiloxanes with chloroalkoxysilanes. Furthermore, they cure slowly when exposed to air, which necessitates storage of assemblies assembled using these compositions in the workshop for at least several weeks. U.S. Pat. No. 3,686,357 discloses a mixture of a diorganopolysiloxane in which each chain end is blocked with a polyalkoxysiloxane unit, an aminoalkylpolysiloxane in which each chain end is blocked with a polyalkoxysiloxane unit, and a curing catalyst. Compositions prepared by the method are described.
However, two types of polysiloxanes are used in these compositions, and the production of each of these polysiloxanes requires specific steps. Furthermore, their viscosity tends to increase during storage. This increase interferes to a considerable extent with extrusion from the nozzle of the cartridge in which they are normally packaged. JP-A-53-102956 discloses an organopolysiloxane containing at least two silicon atoms bonded to alkoxy groups, a crosslinked system obtained by heating an alkoxylated silane, and a tin salt of a carboxylic acid; Compositions made by mixing alkoxylated aminoorganosilanes are described. However, in these compositions, on the one hand, organopolysiloxanes are used which are more difficult to obtain than hydroxylated organopolysiloxanes, and on the other hand, crosslinking systems are used which require heating steps to produce. European Published Patent No. 21859 proposes a single-component CVE composition that can be prepared in a single step by starting directly from a hydroxylated diorganopolysiloxane base polymer and certain polyalkoxysilanes. Great progress has been made. According to this patent, the introduction of functional groups into the hydroxylated basic polymer can be carried out by means of organofunctional silanes, which also act as adhesives. However, these single-component compositions do not have sufficient storage stability. Recently published patents (European published patent no.
No. 69256, No. 104179 and French Patent No. 2543562
This insufficient stability is believed to be due to the presence of residual silanols originating from the hydroxylated base polymer, which do not react with the polyalkoxysilane. Therefore, European Patent Publication Nos. 69256 and 104179 and French Patent No. 2543562 suggest adding a "scavenger" to the CVE composition in order to remove these residual silanols. has been done. Each of these removal agents may be a silane containing a labile hydrolyzable group that preferentially reacts with residual silanol groups, a polysilazane, and an organic compound containing at least one functional group that reacts with silanol groups. can. In the following, the term "stable" is used to refer to single-component CVE compositions containing the alkoxy-terminated organopolysiloxanes of the present invention, which are capable of curing when the mixture is exposed to moisture; It is meant to cure into an elastomer that can remain largely unchanged when protected from atmospheric moisture and is not tacky to the touch even after long storage. In addition, a stable CVE composition is one in which the time it takes for the components of a freshly mixed CVE composition to reach a non-tacky state when touched under atmospheric conditions means that a mixture of the same components is moisture-proof in the absence of moisture. It is also assumed that the storage capacity is substantially the same as when exposed to atmospheric moisture after being stored in a dry container under ambient conditions for an equivalent period of time based on accelerated aging tests at elevated temperatures or for extended periods of time. means. SUMMARY OF THE INVENTION After long and costly research, the applicant has discovered that the deterioration of CVE compositions during storage is primarily due to the presence of condensation catalysts based on metals, in particular tin, in the CVE compositions.
On the other hand, catalysts for introducing functional groups into the hydroxylated oil (i.e. primary or secondary amines, which are
It has been demonstrated that this is due to the simultaneous presence of the hydroxylated base polymer (which acts as a catalyst in the reaction of the polyalkoxysilane with the polyalkoxysilane), even when present in very small amounts in the CVE composition. did it. The present invention provides a stabilizing amount of the CVE composition according to the following formula: {wherein W is a group (CH ₂ ) _o −N=C=O, where n is an integer from 1 to 12}. made it possible to solve problems. In the present invention, the stabilizing amount of the isocyanurate of formula (1) means that the isocyanurate is the first of the functionalized catalysts.
and the amount that reacts with at least all of the secondary amine groups. These amine groups are more reactive than residual silanol or alcohol groups, and if enough isocyanurate is added to react only with these silanol or alcohol groups, these silanol or alcohol groups will react with the isocyanurate. The CVE composition is stabilized even if it remains in the composition without deterioration. This means that the isocyanate group-containing organic This is the first essential difference from the teaching of FR 2543562, which adds compounds. Furthermore, the isocyanurate additive containing isocyanate groups according to the invention has a very low vapor pressure, does not color the CVE composition after heating, is stable up to temperatures that can exceed 220 °C, and is completely miscible with silicones. It has the characteristics of being odorless and non-toxic. As mentioned above, the problem posed by FR 2543562 (removal of residual silanols) is different from the problem posed by the present invention (removal of primary and secondary amine groups); Also, French patent no.
Since many of the stabilizers described in No. 2543562 do not give the desired results of the present invention, the methods described therein are also different. There is no doubt that FR 2543562 describes the use of isocyanate group-containing stabilizers, but it is for a different purpose and this patent describes the use of stabilizers containing isocyanate groups, but it is for a different purpose and this patent Isocyanurates are not mentioned or suggested. Therefore, the present invention provides a method for removing the CVE composition by heating under reduced pressure without necessarily going through an expensive devolatilization step, which does not completely remove the catalyst, especially when the volatility of the catalyst is low. It makes it possible to remove primary and secondary amine groups. In the following, unless otherwise stated, percentages and parts are based on weight. DETAILED DESCRIPTION OF THE INVENTION The present invention more particularly relates to monomers that can be crosslinked at ambient temperature, are stable on storage in the absence of moisture, and can be converted into elastomers in the presence of moisture. A one-component organopolysiloxane composition comprising (i) the following formula: R ² _3-a R ¹ _a Si(OSiR ₂ ) _r SiR ¹ _a R ² _3-a (2) {wherein R is the same R 1 represents a hydrocarbon group containing 1 to 10 carbon atoms, which may be the same or different, and is substituted or unsubstituted with a halogen atom or a cyano group, and R ¹ is the same or different. It's okay to stay on,
represents a C ₁ to C ₁₀ monovalent hydrocarbon group, and the groups R ² may be the same or different;
represents an alkoxy or polyalkoxy group of the formula ZO or ZOEO (where Z represents a C ₁ -C ₄ alkyl group and E represents a C ₂ -C ₄ linear or branched alkylene group) , a is 0 or 1, and the symbol r is 500% at 25°C for the polymer of formula (2).
100 parts of ^at least ^one diorganopolysiloxane _polymer of the following formula _: At least one polyalkoxysilane of the formula (wherein R ¹ , R ² and a have the above meanings):
0 to 15 parts, (iii) inorganic filler: 0 to 250 parts, (iv) condensation catalyst: 0.001 to 3 parts, (v) at least one amino acid containing at least one primary or secondary amine group. organic amines having a pk _b of less than 5 in an aqueous medium and at least one C ₃ - in one molecule bonded to a silicon atom by a SiC bond and having at least one amino group; The amino compound selected from C ₁₅ organic groups and aminoorganosilanes and aminoorganopolysiloxanes simultaneously having both at least one C ₁ -C ₅ alkoxy group or C ₃ -C ₆ alkoxyalkyleneoxy group :
0.001 to 15 parts, (vi) the following formula: At least one isoicinerate of {wherein W is a group (CH ₂ )-N=C=O, where n is an integer from 1 to 12}:
The organopolysiloxane composition is characterized in that it comprises a stabilizing amount. Polymer (i) of formula (2) is obtained by hydroxylating an α,ω dihydroxydiorganopolysiloxane polymer of the following formula: H-(OSiR ₂ ) _r -OH, where R has the same meaning as above. Polysiloxane 1
It is prepared by contacting it with a polyalkoxysilane of formula (3) in a proportion of at least 2 moles per mole. This reaction involves at least one compound (v), such as organic primary and secondary amines (U.S. Pat. No. 3,542,901).
and European Published Patent No. 21859), N,N-
Disubstituted hydroxylamine (French patent no. 2508467)
) or in the presence of aminoorganosilanes (European Publication No. 21859). Viscosity of 700-1000000mPa・s at 25℃,
Preferably 1000-700000Mpa・s at 25℃
The α,ω- _{dihydroxydiorganopolysiloxane} polymer having a viscosity of However, it is not excluded that monoorganosiloxy repeating units of the formula RSiO _1.5 and/or siloxy repeating units of the formula SiO ₂ are present in a proportion not exceeding 2%, based on the number of diorganosiloxy repeating units. 1, substituted or unsubstituted with a halogen atom or a cyano group, represented by the symbol R;
Hydrocarbon groups containing ~10 carbon atoms include: alkyl and haloalkyl groups containing 1 to 10 carbon atoms (e.g. methylethyl, propyl, propyl, isopropyl, butyl , pentyl, hexyl, 2-ethylhexyl, octyl, decyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl and,
cycloalkyl and halocycloalkyl groups containing 1 to 10 carbon atoms (e.g. cyclopentyl, cyclohexyl, methylcyclohexyl, propylcyclohexyl, 2,3 -difluorocyclobutyl and 3,4-difluoro-5
-methylcycloheptyl group), - alkenyl groups containing 2 to 4 carbon atoms (e.g. vinyl, allyl and 2-butenyl groups), - monocyclic aryl and haloaryl groups containing 6 to 10 carbon atoms. (eg phenyl, tolyl, xylyl, chlorophenyl, dichlorophenyl and trichlorophenyl groups), - cyanoalkyl groups in which the alkyl chain part contains 2 to 3 carbon atoms (eg β-cyanoethyl and γ-cyanopropyl groups). Preferred groups are methyl, phenyl, vinyl and 3,3,3-trifluoropropyl groups. Specific examples of repeating units represented by the formula R ₂ SiO include those of the following formulas: (CH ₃ ) ₂ SiO, CH ₃ (CH ₂ =CH)SiO, CH ₃ (C ₆ H ₅ )SiO _, ( _C6H5 ) _2SiO , CF3CH2CH2(CH3)SiO _, NC- _CH2CH2 ( _CH3 ) _SiO , NC- _CH ( _CH3 ) _{CH2 ( CH2} = _CH ) _SiO , NC− _{CH2CH2CH2 ( C6H5} ) _SiO . The polymers used are α,ω- with different molecular weights and/or types of groups bonded to silicon atoms.
It should be understood that it can be a mixture of dihydroxydiorganopolysiloxane polymers. These α,ω-dihydroxydiorganopolysiloxane polymers are commercially available, and furthermore, they can be easily produced using conventionally known methods. By way of example, the diorganopolysiloxane polymer of compound (i) can be blocked at each end of the chain with units of the following formula: (CH ₃ O) ₂ CH ₃ SiO _0.5 , (CH ₃ O ) ₃ SiO _0.5 , (CH ₃ OCH ₂ CH ₂ O) ₂ CH ₃ SiO _0.5 , (CH ₃ OCH ₂ CH ₂ O) ₃ SiO _0.5 , From 0 to 15 parts, preferably from 2.5 to 10 parts, of the polyalkoxysilane (ii) of formula (3) are used per 100 parts of polymer (i) of formula (2). In formula (3), R ¹ represents a C ₁ to C ₁₀ monovalent hydrocarbon group, more specifically a C ₁ to _{C 5} alkyl group (e.g. methyl, ethyl,
propyl, isopropyl, butyl, isobutyl, t-butyl, n-pentyl and isopentyl groups), _-C2 - _C4 alkenyl groups (e.g. vinyl, allyl and 2-butenyl groups), _-C5 - _C8 cycloalkyl groups groups (e.g. cyclopentyl, cyclohexyl and methylcyclohexyl groups), and _C6 - _C10 monocyclic aryl groups (e.g. phenyl,
tolyl and xylyl groups), and R ² may be the same or different and represents an alkoxy or polyalkoxy group as described above. Specific examples of polyalkoxysilanes of formula (3) include those of the following formulas: Si(OCH ₃ ) ₄ , CH ₃ Si(OCH ₃ ) ₃ , CH ₃ Si(OCH ₂ CH ₂ OCH ₃ ) ₃ , Si (OCH ₂ CH ₂ OCH ₃ ) ₄ , CH ₂ = CHSi (OCH ₂ CH ₂ OCH ₃ ) ₃ , C ₆ H ₅ Si (OCH ₃ ) ₃ , C ₆ H ₅ Si (OCH ₂ CH _{2 OCH3} ) ₃ , Si( _OCH3 ) ₂ [OCH( _CH3 ) _{CH2OCH3 ] 2} , _CH2 =CHSi( _OCH3 ) ₃ , _CH2 =CH− _CH2Si ( _OCH3 ) ₃ , _CH2 =C( _CH3 ) _CH2Si ( _OCH3 ) ₃ , Filler (iii) is present in an amount of 0 to 250 parts per 100 parts of polymer (i).
parts, preferably 5 to 200 parts. These fillers can be introduced in the form of very finely divided products (average particle size smaller than 0.1 μm). These fillers include pyrogenic silicas and precipitated silicas whose BET specific surface area is generally greater than 40 m ² /g. These fillers can also be introduced in the form of coarser fractionated products with an average particle size greater than 0.1 μm. Examples of such fillers include:
quartz powder with a specific surface area generally less than 30 m ² /g;
Diatomaceous silica, calcium carbonate, calcined clay, rutile titanium oxide, iron oxide, zinc oxide, chromium oxide, zirconium oxide, magnesium oxide, alumina in various forms (hydrated or non-hydrated), boron nitride, lithopone, Mention may be made of barium metaborate, barium sulphate and batilloni. The surface of these fillers can be modified by treatment with various organosilicon compounds. The organosilicon compounds are those commonly used for this purpose and are therefore organochlorosilanes, diorganocyclopolysiloxanes, hexaorganodisiloxanes, hexaorganodisilazanes or diorganocyclopolysiloxanes (FR 1126884). No. 1136885, No. 1236505
and British Patent No. 1024234).
In most cases, the treated filler contains 3 to 30% by weight of organosilicon compounds. These fillers can consist of a mixture of several fillers with different particle size distributions. Thus, for example, these include 30-70% finely divided silica with a BET specific surface area greater than 40 m ² /g and 70-30% more coarsely divided silica with a specific surface area less than 30 m ² /g. It can consist of As condensation catalyst (iv) it is possible to use at least one metal compound known to the expert, in particular a compound of a metal selected from iron, lead, tin, titanium and zirconium. The preferred metal is tin, for example in the form of tin monocarboxylate and tin dicarboxylate such as tin 2-ethylhexanoate, dibutyltin dilaurate and dibutyltin diacetate {Knoll (No. 11) Chemistry. Chemistry and Technology of Silicones,
2nd edition (1968), Academic Press, p. 337}. Particularly suitable are hexacoordinate chelates of valent tin, such as those described in European Patent No. 147,323 and US Pat. No. 4,517,337. Also, - Diorganotin bis(β-diketonate) and - A valent organic derivative of tin that does not contain a β-diketonato group and contains at least one tin atom, in which each tin atom forms a Sn-C bond. by a group selected from organic or inorganic groups, halogen atoms, hydroxyl groups, and oxygen atoms, which have two organic groups bonded together, and the remaining two valences are bonded by SnO or SnS bonds. Preference is also given to condensation catalysts which are mixtures with the above-mentioned derivatives. Said organic derivatives of valent tin which do not contain β-diketonato groups can in particular be tin salts corresponding to the following formulas: A ₂ SNR ⁶ ₂ , R ⁶ ₂ SnO, AR ⁶ ₂ SnOSnR ⁶ ₂ A, {In the formula, R ⁶ represents a C ₁ to C ₂₀ halogenated or non-halogenated hydrocarbon group, and A is a halogen atom or Sn-O or Sn-
represents an organic or inorganic group bonded to the tin atom by an S bond, Q represents a C ₂ to _{C 10} alkylene group, and A has the formula R ⁷ COO (where R ⁷ is C ₁ to representing a C ₂₀ halogenated or non-halogenated hydrocarbon group), a monocarboxylate group of formula (2e)

A dicarboxylate group of the formula (which is bonded to the same tin atom or two tin atoms and has the following two formulas: (where G ¹ represents a C ₁ -C ₁₅ hydrocarbon group and R ⁷ has the same meaning as given in (e) above), (3e) formula R ⁷ OCOG ¹ COO (wherein R ⁷ and G ¹ have the same meanings as given in (e) and (2e) above, respectively). The above-mentioned tin salts are known compounds, particularly in the above-mentioned Knoll book, U.S. Pat. No. 3,186,963;
3862919, Belgian Patent No. 842305 and British Patent No. 1289900. As compounds (v) containing primary or secondary amine groups, organic amines, aminoorganosilanes and aminoorganopolysiloxanes can be used. Among the organic amines, aliphatic amines, cycloaliphatic amines, heterocyclic amines and arylaliphatic amines can be used. Specific examples of aliphatic amines include: n-butylamine, of the following formula: _CH3 -CH-C( _CH3 ) _2NH2 amylamine, n-hexylamine, n _- decylamine, laurylamine, hexadecylamine, n-octylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di- -n-hexylamine, ethylenediamine, propylenediamine, hexamethylenediamine, and the following formula _{H ( NHCH2CH2} ) _2NH2H ( _{NHCH2CH2 ) 3NH2H2NCH2CH} ( _{NH2 ) CH2NH2 polyvalent amine .} Specific examples of alicyclic amines include: cyclopentylamine, cyclohexylamine and the following formula:

【formula】 amine. Specific examples of heterocyclic amines include: piperidine, pyrrolidine, piperazine and the following formula:

【formula】

An amine with the formula: Specific examples of arylaliphatic amines include benzylamine and phenylethylamine. All of these organic amines are known,
Methods for their production are also known. Furthermore, many of these are commercially available. Compound (v) also contains at least one C _{3 -C} bonded to a silicon atom through a SiC bond and substituted with at least one amino group belonging to a primary or secondary amine in one molecule. selected from at least one aminoorganosilane and aminoorganopolysiloxane having both ₁₅ organic groups and at least one C1 _{- C5} alkoxy group or _C3 - _C6 alkoxyalkyleneoxy group. You can also do it. Specific examples of organoaminosilanes include those of the following formula in which the organic group substituted with at least one amino group is a hydrocarbon group: H ₂ N(CH ₂ ) ₃ Si(OCH ₂ CH ₂ OCH ₃ ) ₃ , H ₂ N(CH ₂ ) ₃ Si(OCH ₃ ) ₃ , H ₂ N(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ , H ₂ N(CH ₂ ) ₄ Si(OCH ₃ ) ₃ , _{H2NCH2Si ( OCH3} ) ₃ , _HN (n- _C4H9 ) _CH2Si ( _OCH3 ) ₃ , The preparation of these silanes is more particularly described in US Pat. Specific examples of organoaminosilanes include those of the following formula in which the organic group substituted with at least one amino group is a hydrocarbon having an ether or thioether bond: H ₂ N(CH ₂ ) ₃ O(CH ₂ ) ₃ Si(OCH ₂ CH ₂ OCH ₃ ) ₃ , H ₂ N(CH ₂ ) ₃ O(CH ₂ ) ₃ Si(OCH ₃ ) ₃ , C ₂ H ₅ NH(CH ₂ ) ₃ O( _CH2 ) _3Si ( _{OCH3 ) 3} , _{H2NCH2CH ( CH3} ) _CH2O ( _CH2 ) _{3 SiC6H5}
(OCH ₃ ) ₂ , H ₂ BCH ₂ CH ₂ NH (CH ₂ ) ₃ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ S (CH ₂ ) ₃ Si (OCH ₂ CH ₂ OCH ₃ ) ₃ , H ₂ N(CH ₂ ) ₂ S(CH ₂ ) ₃ Si(OCH ₃ ) ₃ , H(NHCH ₂ CH ₂ ) ₂ S(CH ₂ ) ₃ Si(OCH ₃ ) ₃ . The production of these silanes is specifically described in U.S. Patent No.
It is described in No. 3341563, No. 3551375, No. 3598853, and No. 3488373. Aminoorganopolysiloxanes that can be used are the aminoorganosilanes mentioned above, more particularly for example those of the following formula: H ₂ N(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ H ₂ N(CH ₂ ) ₃ Trialkoxylated aminoorganosilanes such as Si(OCH ₃ ) ₃ H ₂ N(CH ₂ ) ₃ NH(CH ₂ ) ₃ Si(OCH ₃ ) ₃ and dihydroxydioxysilanes belonging to the class of polymers of formula (4) above. It can be produced by condensing with organopolysiloxane. The aminoorganopolysiloxanes produced according to the invention are particularly useful in US Pat.
No. 1385693 and No. 2228814. In order to improve the adhesion, the composition according to the invention contains (i) per 100 parts at least one molecule bonded to the silicon atom by SiC bonds and belonging to tertiary amine and/or guanidino groups. at least one substituted with one amino group
at least one aminoorganosilane or aminoorganosilane having both _C3 - _C15 organic groups, and at least one _C1 - _C5 alkoxy group or _C3 - _C6 alkoxyalkyleneoxy group. 0.5 to 10 parts of polysiloxane (vii) (eg, guanidinoorganosilanes and guanidinoorganopolysiloxanes as described in US Pat. No. 4,180,642) can also be included. As adhesion promoter (vii), in particular the following formula: (wherein the groups Y may be the same or different and are alkyl or alkoxy groups containing 1 to 4 carbon atoms, at least two of the groups Y are alkoxy groups, Y′ may be the same or different;
Silanes selected from hydrogen atoms and alkyl groups containing from 1 to 3 carbon atoms, where s is an integer from 3 to 10, are suitable. As the silane of formula (5), γ-morpholinopropyltrimethoxysilane・γ-morpholinopropyltriethoxysilane can be mentioned. These compounds and their preparation methods are described in the Journal of the Organic Chemistry by John L. Speier,
It is described in Volume 36, No. 21 (1971), page 3120. Isocyanurate of formula (1) is a known compound, and its production method is particularly described in European Patent Publication No.
Described in No. 57653. Preferred isocyanurates include n in W in formula (1).
from 4 to 8, especially those with n=6 (which are commercially available from Rhone-Poulenc under the registered trade name "Tolonate HDT"). The stabilizing amount of the compound is the amine
It depends on the amount of (v) used, the optional devolatilization of polymer (i) and the volatility of the amine. Generally, a compound of formula (1) per 100 parts of polymer (i)
0.01 to 5 parts can advantageously be used. The present invention also provides a method for preparing CVE compositions according to which one mole of a polymer of formula (4) is prepared under anhydrous conditions in the presence of a catalytically effective amount of compound (v). Polymer (i) is prepared by reacting with at least 2 moles of polyalkoxysilane, and after reaction and optional devolatilization, the compounds (ii), (iii), (iv), (v), (vi) and (vii) are introduced. Examples Example 1 The following were mixed in a blender under anhydrous conditions: 100 parts α,ω-dihydroxydimethylpolysiloxane with a viscosity of 20000 mPa·s at 25°C and a hydroxyl content of 750 ppm. 7 parts of silicon methyl and 0.2 parts of piperidine. Heat this mixture to 80 °C for 40 minutes, then
Devolatilization was carried out by stirring under a vacuum of 0.133 kPa. Methanol produced by the reaction of methyl silicate with the silanol in the silicone oil, excess methyl silicate and piperidine are removed by this devolatilization. However, by polarographic analysis it can be demonstrated that approximately 0.0150 parts of piperidine remain per 100 parts of the reaction mixture and that these last traces of amine are very difficult to remove by devolatilization alone. . The mixture was allowed to cool and 0.15 parts of dibutyltin dilaurate and various amounts of Tolonate HDT were added. The composition was protected from moisture and divided into 6 batches. The first batch was applied in open air in a 2 mm thick layer onto a polyethylene plaque previously coated with a commercial detergent. The curing time was evaluated by recording the time t (minutes) required for the layer to become non-tacky to the touch. According to NF standard T-51109, the Shore A hardness of the film after 2 or 7 days (SAH 2 days and
SAH7 days) and in some cases NF standard T
-46002, the tensile strength TS (MPa) and elongation at break EB (%) were measured. The remaining five batches of the compositions were subjected to accelerated aging tests by placing them in an oven at a temperature of 100 DEG C. for various times under an anhydrous atmosphere. At the end of the test, after cooling to room temperature, measurements were carried out as in the first batch. The results are summarized in Table 1 below. In the table,
Amounts of Tolonate HDT are given in parts per 100 parts of original hydroxyl or oil.

[Table] From Table 1, by accelerated aging at 100℃
Without the addition of Tolonate HDT, the curing time is increased and the hardness of the crosslinked product is reduced and the composition exhibits excellent stability even after 48 hours accelerated aging test at 100°C. It can be seen that the presence of only a small amount of Tolonate HDT is sufficient to effect this effect. Also,
It can also be seen that large amounts of Tolonate HDT increases curing time (possibly due to Tolonate HDT trapping water). Example 2 Except for not carrying out the devolatilization process,
The procedure of Example 1 was repeated. The resulting reaction mixture contains all of the methanol produced and all of the amine added, thus containing a large amount of Tolonate HDT.
was added. The results are summarized in Table 2 below.

Table 2 It can be seen that Tolonate HDT gives good stability even after accelerated aging test. Example 3 Piperidine per 100 parts of the reaction mixture after devolatilization
Example 1 was repeated except that 0.085 part remained in the reaction mixture. The following were added to 100 parts of the reaction mixture: - Methyl silicate: 1 part - γ-morpholinopropyltrimethoxysilane: 3 parts - Pyrolysis method treated with octamethylcyclotetrasiloxane, BET specific surface area 60 m ² /g Silica: 10 parts Dibutyltin dilaurate: 0.15 parts and Tolonate HDT: various amounts. After carrying out an accelerated aging test at 100° C. for 2 days on the resulting composition, which is non-flowing and adheres to various substrates, or without carrying out this test, the composition shown in Example 1 was prepared. We carried out similar measurements. The results obtained are summarized in Table 3 below. In the table, the amount of Tolonate HDT is given in parts per 100 parts of original hydroxyl or oil. It can be seen from Table 3 that by adding Tolonate HDT it is possible to obtain CVE compositions with the same properties with or without accelerated aging testing.

[Table] Example 4 In this example, the following ingredients are mixed and heated to 80℃.
The procedure of Example 1 was repeated with heating for 20 minutes at 100 parts of α,ω-dihydroxydimethylpolysiloxane having a viscosity of 20 000 mPa·s at 25° C. 7 parts of methyl silicone 0.2 parts of piperidine. After cooling to 20-25° C., the following were added: 2 parts of γ-morpholinopropyltrimethoxysilane Pyrogenic silica with a BET specific surface area of 60 m ² /g treated with octamethylcyclotetrasiloxane: 10 parts Dibutyltin dilaurate: 0.15 parts Tolonate HDT: 0 or 1.5 parts. The same measurements as in Example 3 were carried out. The results are summarized in Table 4 below.

Table 4 It can be seen from Table 4 that the properties of the composition do not change after the accelerated aging test only when Tolonate HDT is added. Example 5 The operation of Example 4 was repeated using the following various components: α·ω-dihydroxydimethylpolysiloxane with a viscosity of 175000 mPa·s at 25°C: 100 parts Methyl silicate: 8 parts Di- n-hexylamine 0.5 part. After heating to 80°C for 45 minutes, the following were added: 3 parts of γ-morpholinopropyltrimethoxysilane.
30 parts of pyrogenic silica with a BET specific surface area of 150 m ² /g:
9 parts Calcium carbonate with an average particle size of 5 μm: 35 parts Dibutyltin dilaurate: 0.1 part Tolonate HDT: 0 or 1.5 parts. The same measurements as in Example 4 were carried out. The results are summarized in Table 5 below. From this table,
It can be seen that Tolonate HDT has a stabilizing effect.

【table】

Claims (1)

Claims: 1. A monolithic organopolysiloxane composition capable of crosslinking at ambient temperature, stable on storage in the absence of moisture, and convertible to an elastomer in the presence of moisture. , (i) The following formula: R ² _3-a R ¹ _a Si(OSiR ₂ ) _r SiR ¹ _a R ² _3-a (2) {In the formula, R may be the same or different, Represents a hydrocarbon group containing 1 to 10 carbon atoms substituted or unsubstituted with a halogen atom or a cyano group, R ¹ may be the same or different, and C ₁
~ represents a C ₁₀ monovalent hydrocarbon group, and the groups R ² may be the same or different,
represents an alkoxy or polyalkoxy group of the formula ZO or ZOEO (where Z represents a C ₁ -C ₄ alkyl group and E represents a C ₂ -C ₄ linear or branched alkylene group) , a is 0 or 1, and the symbol r is 500 to 500% at 25°C for the polymer of formula (2).
100 parts of ^at least ^one diorganopolysiloxane _polymer of the following formula _: At least one polyalkoxysilane of the formula (wherein R ¹ , R ² and a have the above meanings):
0 to 15 parts, (iii) inorganic filler: 0 to 250 parts, (iv) condensation catalyst: 0.001 to 3 parts, (v) at least one amino acid containing at least one primary or secondary amine group. organic amines having a pk _b of less than 5 in an aqueous medium and at least one C ₃ - in one molecule bonded to a silicon atom by a SiC bond and having at least one amino group; The amino compound selected from C ₁₅ organic groups and aminoorganosilanes and aminoorganopolysiloxanes simultaneously having both at least one C ₁ -C ₅ alkoxy group or C ₃ -C ₆ alkoxyalkyleneoxy group :
0.001 to 15 parts, (vi) the following formula: At least one isocyanurate of {wherein W is a group (CH ₂ ) _o −N=C=O, where n is an integer from 1 to 12}:
The organopolysiloxane composition comprising a stabilizing amount. 2. The composition according to claim 1, wherein n in the group W in formula (1) of compound (vi) is 4 to 8. 3. The composition according to claim 2, wherein n is 6. 4. The composition according to any one of claims 1 to 3, characterized in that 0.01 to 5 parts of compound (vi) is used. 5. The composition according to any one of claims 1 to 4, wherein the compound (iv) is a tin compound. 6 At least one C3 to _C15 organic group bonded to a silicon atom through a SiC bond in one molecule and substituted with at least one amino group belonging to a tertiary amine and _/ or a guanidino group and - at least one C ₁ to C ₅ alkoxy group or
At least one aminoorganosilane or aminoorganopolysiloxane compound having both _C3 to _C6 alkoxyalkyleneoxy groups
(vii) The composition according to any one of claims 1 to 5, further comprising 0.5 to 10 parts. 7 Compound (vii) has the following formula: (wherein the groups Y may be the same or different and are alkyl or alkoxy groups containing 1 to 4 carbon atoms, provided that at least two of the groups Y are alkoxy groups, The groups Y′ may be the same or different;
selected from hydrogen atoms and alkyl groups containing 1 to 3 carbon atoms, s being an integer from 3 to 10)
Compositions as described in Section. 8 The condensation catalyst is: diorganotin bis(β-diketonate) and an organic derivative of valent tin containing no β-diketonato group and containing at least one tin atom, each tin atom being Sn-C A group having two organic groups bonded by a bond, and the remaining two valences are selected from an organic or inorganic group bonded by a SnO or SnS bond, a halogen atom, a hydroxyl group, and an oxygen atom. 8. A composition according to any one of claims 1 to 7, characterized in that it is a mixture with said derivative which is thus saturated.